Material surface treatment method using concurrent electrical and photonic stimulation

ABSTRACT

A material surface treatment protocol uses concurrent electrical, vibrational, and photonic stimulation to generate an exothermic reaction and coat the surface of a material, such as palladium. This protocol is performed at or near the boiling point of water within a sealed vessel that prevents the escape of steam and that is lined with silica or a similar glass to increase the silica available to the reaction. The great majority of the applied energy is heat used to elevate the temperature to near the boiling point, while concurrent stimulations provide only about 100 mW of additional energy for the surface treatment.

TECHNICAL FIELD

The invention relates to surface treatment of materials, and in particular to preparation of the surface of a material in a liquid medium in order to facilitate certain desirable exothermic reactions using such material.

BACKGROUND ART

U.S. Pat. No. 7,442,287 describes a surface treatment method of preparing materials, such as palladium, at or near their surfaces in order to facilitate their use, e.g., for generating exothermic reactions. In that treatment method, a solution in water of an electrolyte, a surfactant, and a pH-adjusting agent (to maintain the pH of the solution between 6.5 and 8.9) is heated to and maintained at or just below the boiling point in an open glass beaker. A pair of electrodes, at least one of which has the surface to be treated, is immersed in the solution with a gap between them. The electrodes are then electrically (and vibrationally) stimulated as a series of pulses, while simultaneously being photonically stimulated by a light source. Scanning electron microscope (SEM) images of the treated electrodes show that the concurrent stimulations of the electrode material while immersed in the hot solution form crater sites on the electrode surface and leave a silica coating with a stratified and sponge-like texture.

The metallic surface treated by the method provides enhanced sites for facilitating desired reactions, e.g., hydrogen absorption and release, hydrogenation, catalytic reactions, and exothermic reactions. Palladium, e.g., is known to have a large capacity for hydrogen storage and release, useful for fuel cells and the like, the level of performance of which depends on the presence of certain surface sites for efficient hydrogen exchange.

SUMMARY DISCLOSURE

The present invention is an improvement of our previous method set forth in the aforementioned '287 patent. Similar to before, the protocol consists of a specific series of steps applying electrical and photonic stimuli between conductive electrodes immersed in a solution containing lithium sulfate as an electrolyte and a silica compound while that solution is maintained at an elevated temperature at or near the boiling point.

As the work on the protocol described in our previous patent has progressed, we have moved it from an open glass beaker into a sealed vessel to prevent the escape of steam, along with other constituents in the solution or reaction products. As higher temperature boiling points were obtained under pressure, the treatment protocol proved to be more robust when taking place in such a sealed container with specific refinements.

Having the treatment reactions occur in the presence of silica or glass proved to be very beneficial. In particular, we obtained better results (1) when we lined the inner surface of the reaction vessel with a glass beaker, (2) when we put a quartz cap over the beaker, (3) when we replaced our stainless-steel thermocouple wells with glass ones, and (4) when we threaded glass beads onto the electrodes. Additionally, the solution contained either a soluble form of silica or a silica compound in suspension. When conducted in such a glass vessel, the use of a DC stimulus and a vibrational stimulus in the protocol proved to be optional.

The electrode material immersed in the hot solution is subject to electrical and photonic stimulation. It has been found that the treatment works better when some RF frequencies are used as electrical stimuli than others, indicating a possible resonance phenomenon that has proved to be beneficial. Stimulating the system at one or more resonant frequencies can cause the underlying oscillation to amplify. In particular, an effective RF electrical stimulus was shown to be an amplified replication of a signal emitted during the reaction, which was a 43.4 MHz sine wave added to a 3.1 MHz sine wave.

Temperature spikes were observed with electrodes made of four different metals: palladium, silver, platinum, and gold, and using three different silica compounds: anionic silica hydride, lithium metasilicate, and sodium silicate.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a data log for a first experiment using a palladium electrode in a heavy water solution and being stimulated in accord with the method of the present invention.

FIG. 2 is an SEM photo of an electrode surface resulting from treatment by the protocol recorded in FIG. 1.

FIGS. 3, 4, and 5 are respective Energy Dispersive Spectrometry (EDS) spectral analyses of the deposited layer and bare metal for the treated electrode surface and of the cross-sectioned electrode.

FIGS. 6, 7, and 8 are SEM photos of the cross-sectioned electrode coating (6 and 7) and of the electrode metal itself (8).

FIGS. 9 and 10 are EDS spectral analyses of the sectioned electrode metal.

FIG. 11 is a data log for a replication of the test protocol, using a palladium electrode in a solution of anionic silica and lithium sulfate in heavy water, and stimulated with a modulated pulse stream.

FIG. 12 is a table of atomic concentrations for the electrode obtained from Auger analysis after conclusion of the protocols for FIGS. 3-10.

FIG. 13 is a data log for a replication of the test protocol, again using a palladium electrode in a heavy water solution and stimulated in accord with the present invention.

FIG. 14 is an EDS spectral analysis of the electrode resulting from the protocol for FIG. 13.

FIGS. 15, 16, and 17 are respective data log, and SEM photos of two pieces of the wire for another experiment using glass beads threaded over palladium electrodes in a heavy water solution and stimulated in accord with the present invention.

FIG. 18 is a data log for yet another experiment conducted using glass-bead-threaded palladium electrodes, but in a light water solution and stimulated in accord with the present invention.

FIGS. 19 and 20 are data logs for experiments of the surface treatment method respectively using silver and platinum electrodes in heavy water.

FIGS. 21 and 22 are data logs for experiments of the surface treatment method, using palladium electrodes in heavy water, wherein lithium metasilicate and sodium silicate, respectively, were dissolved in the solution.

FIG. 23 is an SEM photo and accompanying EDS spectrum for the electrode resulting from the experiment corresponding to FIG. 22.

FIG. 24 is a data log for an experiment using a palladium electrode in a solution of lithium metasilicate and lithium sulfate in heavy water, and stimulated with a modulated pulse stream.

FIG. 25 is a data log for an experiment using a palladium electrode in a solution of lithium metasilicate and lithium sulfate in heavy water, and stimulated with a 3.1 MHz sine wave added to a 43.4 MHz sine wave.

FIG. 26 is a SEM photo of an electrode used in that experiment.

DETAILED DESCRIPTION

The treatment protocol is performed in an electrolytic cell consisting of two or more electrodes, composed of similar or dissimilar metals, for example of palladium, silver, platinum, or gold, or even conductive material other than metal. One or more of the electrodes have material surfaces to be treated. At least one of the electrodes may be coated with silica or a silicate, threaded with silica or glass beads, or the electrode may consist of sintered metal and silica. The electrodes are immersed in a solution or suspension of an electrolyte in a liquid, such as heavy water (D₂O), lithium sulfate (Li₂SO₄), and a silica compound either in solution or in suspension. Alternatively, less active results have also been observed using light water (H₂O). A combination of both light and heavy water could also be used. A pH-buffering agent, as used in our aforementioned '287 patent, was found to be optional. If used, the buffering agent might comprise either EDTA or citric acid in quantities sufficient to maintain a pH in a range from 6.5 to 8.9.

As before, the electrolytic cell may be of any size needed to accommodate a work piece whose surface is to be treated by this protocol. However, now the vessel used in our experiments was a stainless steel cylinder with a central well 2 inches deep and 2 inches in diameter, having a closed bottom and a removable top. Ultimately, it was dimensioned to accommodate a glass beaker capped with a quartz top. Alternatively, the vessel may be a glass- or silica-lined metallic vessel. The vessel could also be lined with a piezoelectric material, in the form, e.g., of a porcelain glaze. A sealed vessel prevented the escape of steam, along with other constituents in the solution or reaction products, and allowed higher temperature boiling points to be obtained under pressure. The sealed vessel also made it much more practical to instrument the experiments and to data log their results. Holes in the top allowed electrodes and thermocouples to pass through it, while sealed glass ports in the vessel wall allowed for the concurrent photonic stimulation by exterior illumination. The vessel weighed more than five kilograms, thereby providing considerable thermal mass to ensure that measured temperature transients were generated within the vessel and not the result of external impulses. As a safety practice appropriate when working with exothermic reactions in a sealed vessel at or near the boiling point of water, our vessel was equipped with a pair of pressure relief valves set to lift sequentially at different pressures.

An embodiment of the surface treatment method in accord with the present invention uses either of two commercial products called “MegaH-” and “Super Hydrate”, as one source of silica with which the electrodes to be treated are in intimate contact. These compositions are respectively the powdered and dissolved form of an anionic silica hydride. The following points can be made about these two products: They are described in their marketing literature as 1) an anionic hydride organosiloxane; 2) a silsequioxane having hydroxyl-terminated constituents; 3) sources of ionized hydrogen contained within soluble microclusters of silica hydride; and 4) consisting of tetrahedral frameworks that encapsulate hydrogen cations. Pure samples of the products without additives were not available. According to its package label, Mega H- has potassium citrate, potassium carbonate, and oleic acid added. Super Hydrate has potassium carbonate, magnesium sulfate, and oleic acid added.

Alternative embodiments of the surface treatment method in accord with the present invention have as sources of silica either sodium silicate Na₂SiO₃ in solution, or lithium metasilicate Li₂SiO₃ in suspension. A chelating agent, such as EDTA, may be used to facilitate the suspension of the silica compound.

The liquid within the vessel was blanketed during the experiments with one or a combination of hydrogen and helium gases, for example in approximately equal percentages, which were introduced through two inlet valves. The atmosphere was vented through an outlet valve. The saturation of the liquid with these gases is optional.

A heating coil was located in a cavity in the bottom of the vessel, and its input voltage and current measured to monitor input power. The temperature of the vessel was first raised to 102° C.±1°, then maintained until the temperature of the liquid had remained stable near the boiling point over an hour or more to establish a thermal equilibrium. A pair of thermocouples monitored the temperature of the liquid via thermocouple wells projecting into the liquid. The wells were first made of stainless steel and later of glass. The thermocouples also passed through the vessel's cap via Teflon® seals compressed with Swagelok® fittings.

Through experimentation, it was determined over time that the exothermic reaction had a characteristic and readily identifiable heat signature. In later experiments, there was less concern about establishing thermal equilibrium and the temperature was driven more quickly to the operating range of the reaction and it was stimulated sooner. No attempt was made to make calorimetric measurements; the temperature transients were judged to be sufficient evidence of heat generation.

Two or more electrodes were immersed in the liquid. The work piece or pieces to be treated are used as one or more of these electrodes, which can be of any shape and size, such as that of a nozzle. The material being surface treated by this method may be a conductive material such as a solid metal or alloy, containing for example palladium, or may be metallically plated with the desired surface material. Any of the electrodes may also be surface coated with other materials, such as silicates or polymers (such as polytetrafluoroethylene), with either the underlying metal or the coating or both to be treated by the protocol.

RF electrical and photonic stimuli were applied in manner similar to that previously described in our earlier patent. For example, in some of our experiments, the electrical stimuli were provided via three palladium wires of 0.025″ diameter: an anode for the RF stimulus, a second anode for the DC stimulus, and a common cathode. The electrodes formed a triangle with sides 0.9, 1.45, and 1.45 inches long. The shortest side lay between the RF anode and the common cathode. The electrical stimulation may, therefore, consist of either or both direct current and alternating current, where the alternating current can be modulated with frequencies in the RF range, preferably including frequencies that coincide with absorptive spectra of components of the solution. The electrical stimulation may be a combination of direct current voltage and alternating current voltage applied, either concurrently or sequentially, between either separate anodes or a common anode and a common cathode. The electrodes and the thermocouples were equally spaced on a bolt circle, so thermocouples would be 0.9 and 1.45 inches away from the cathode. All electrodes were isolated from the vessel and sheathed in glass tubing to the surface of the liquid in order to keep them straight and to concentrate the RF stimulus in the liquid. The electrodes passed through the vessel's top via Teflon® seals compressed with Swagelok® fittings.

Four “Ultrabright” white light-emitting diodes (LEDs) capable of generating 15,000 mcd were spaced equally around the vessel below the surface of the liquid as photonic stimuli. These stimuli were provided through sealed glass ports in the vessel wall. The LEDs are intensity-modulated with pulses during the same period when the electrical stimulation is applied. Electrical and photonic stimulation may be applied either concurrently or sequentially.

Having the treatment reactions occur in the presence of silica or glass proved to be very beneficial. Attempts to run the protocol directly within vessels of stainless steel and Teflon® were not successful. We obtained better results (1) when we lined the inner surface of the reaction vessel with a glass beaker, (2) when we put a quartz cap over the beaker, (3) when we replaced our stainless-steel thermocouple wells with glass ones, and (4) when we threaded glass beads onto the palladium wire electrodes. When conducted in such a glass vessel, the use of a DC stimulus in the protocol proved to be optional.

Additionally, our solution contained a form of silica. We had noted that the first step in the protocol described in our earlier patent consisted of heating the solution until the bubbles had cleared from its surface. Those bubbles, of course, were characteristic of surfactants, and the anionic silica hydride had originally been chosen for its surfactant properties. However, the disappearance of the bubbles indicated that the surfactant properties had also diminished or disappeared. What was left was silica plus any additives present in the original surfactant composition.

The protocol typically requires at least two hours of treatment before bursts of heat are observed. It is suspected that something must be happening to either the solution or to the electrodes in that period to facilitate the observed reaction. Lithium salts, such as lithium sulfate (Li₂SO₄), are used as an electrolyte in the solution. Since the reaction does not occur immediately, it is possible that the silica and the lithium in our protocol are bonding in some way before the bursts of heat are observed. In particular, the lithium may. be combining with the silica compound in the solution over the time frame of the treatment protocol to form a lithium silicate, possibly one or more of Li₄SiO₄ (lithium orthosilicate), Li₆Si₂O₇, Li₂SiO₃ (lithium metasilicate), LiSi₄O₇, or Li₄Si₃O₈; or since silsesquioxanes were used as the anionic silica hydride surfactant in the solution for the experiments, perhaps the lithium is bonding to resulting siliceous cage structures when that compound is used as the source of the silica.

It was also found that the treatment works better when some RF frequencies are used as electrical stimuli than others and that the protocol yielded heat bursts in the sealed vessel in more or less time when different frequencies were used as stimuli. Given how important the presence of silica is to the effectiveness of the treatment protocol, it is speculated that certain natural frequencies of vibration of the silica bonds in the solution are being driven to vibrational resonance by the RF electrical stimuli, the photonic stimuli, or both. As a general statement, resonance is the tendency of a system or phenomena to oscillate at larger amplitude at some frequencies than others. Such systems and phenomena absorb energy at these resonant frequencies, such that stimulating a system or a phenomena at a resonant frequency or set of resonant frequencies can cause the underlying oscillation to amplify, often dramatically so. For example, the electrical stimulation may comprise one sinusoidal signal having a frequency between 1 MHz and 20 MHz added to another sinusoidal signal having a frequency between 25 MHz and 100 MHz. When viewed with an Agilent 4195A spectrum analyzer, one of the effective RF electrical stimuli described in the '287 patent was shown to be a rich comb of spectra in the range of 1 MHz to 200 MHz, spaced at 6.2 MHz and having peaks in the profile of the spectral comb at 3.1 MHz and 50 MHz, which were the frequencies of the underlying pulses and the sinusoidal modulation of those pulses. That stimulus provided literally dozens of spectra that could have been at resonant frequencies. The electrical stimulation may comprise a replication of electrical energy emitted during a desired exothermic reaction, but with greater amplitude.

Some experiments were conducted in a glass vessel of similar dimensions to the steel one described above that permitted the reaction to be observed as it was taking place. During the reaction, the RF stimulus was turned off and an attempt made to capture any signals emitted by the reaction with an Agilent model DSO5054A high-speed digitizing oscilloscope. Although the emitted signals proved to be very transient and elusive, one of them was captured. It resembled a 43.4 MHz sine wave added to a 3.1 MHz one, distorted by considerable noise. Subsequently, a cleaner version of that signal generated by an Agilent 81150A waveform generator was used as a stimulus to the reaction. That stimulus proved to be effective.

Similar reasoning could be applied to any resonances for the photonic stimulus.

The specific steps of a representative protocol are shown below:

-   Step 1. Prepare a solution beginning with 30 ml of heavy water (D₂O)     in an open beaker. Light water (H₂O) can be used, but will have a     lower boiling point and generate a less robust reaction. Add an     electrolyte of 110 mg of Lithium Sulfate Monohydrate (Li₂SO₄.H₂O).     Another lithium salt could be used. Add 40 mg of lithium     metasilicate (Li₂SiO₃). Alternatively, one can use an unadulterated     form of anionic silica hydride in equivalent amounts, if available.     Other forms of silicates might be used instead or in addition, such     as lithium or sodium silicate. The solution with lithium     metasilicate will be basic. Buffer the solution with EDTA, which is     a chelating agent that has surfactant properties, until it has a pH     within the range of 6.5 to 8.9. The lithium metasilicate is     insoluble, and the EDTA serves to dissolve it or bring it into     suspension. -   Step 2. Immerse two or more spaced apart electrodes, e.g., of     palladium wire, into the solution. In the case of palladium wire,     the electrodes are preferably immersed to at least 1.0 cm depth, are     separated by a gap at a distance of 2.3 cm. At least one of the     electrodes will have a surface to be treated by the protocol. The     electrode(s) to be treated are also preferably threaded with silica     or glass beads to provide intimate contact with another source of     silica. -   Step 3. Then condition the surface of the electrodes with the     following process: Stimulate electrodes immersed in the liquid with     electrical and photonic stimuli while the solution is at a     temperature between 90° and 100° C. Stir and/or swirl gently (e.g.,     with a magnetic stirrer) to keep the lithium metasilicate in     suspension. The electrical stimulation may preferably consist of a     43.4 MHz sine wave added to a 3.1 MHz one with an amplitude of 8     Volts when driven from two 50-ohm differential outputs. This signal     was generated with an Agilent 81150A arbitrary waveform generator.     When this stimulus is applied to the electrodes, the impedance     across them will vary depending upon the characteristics of the     solution. Simultaneously photonically stimulate the electrodes and     the gap between them using, e.g., two banks of five white     “Ultrabrite” LEDs with a maximum luminous intensity of 15,000 mcd     each. The LEDs are preferably pulse-modulated by frequency-hopping     through the following six frequencies, dwelling at each for five     minutes: 464, 1234, 1289, 2008, 3176, and 5000 Hz with 50% duty     cycles. Continue stimulating concurrently with both electrical and     photonic stimuli at an elevated temperature for fifteen minutes.     After fifteen minutes, substitute a 4 Volt DC stimulus for the     time-varying one and apply it for five minutes. After that, re-apply     the time-varying one for fifteen more minutes, followed by reversing     the polarities of the DC one and applying it for five minutes.     Additionally, monitor the solution temperature with the     thermocouples throughout this conditioning process to keep the     solution within the preferred range of 90° to 100° C. -   Step 4. Transfer the solution from the open beaker to a sealed     vessel. The pH may have shifted during the conditioning process. If     it has, buffer it with EDTA or an appropriate base to bring it back     into the preferred range of 6.5 to 8.9. Install the electrodes in     the vessel. Seal the vessel and introduce a blanket of helium and     hydrogen gases above the solution to create saturation with those     gases and to maintain such saturation for the duration of the     protocol. Then heat the solution to bring it to a temperature within     2° C. of the boiling point and to maintain that elevated temperature     for the duration of the protocol. -   Step 5. Then treat the surface of the electrodes with the following     process: Stimulate electrodes immersed in the liquid with a     time-varying electrical signal. The electrical stimulation may again     preferably consist of a 43.4 MHz sine wave added to a 3.1 MHz one     with an amplitude of 8 Volts when driven from two 50-ohm     differential outputs. This signal was generated with an Agilent     81150A arbitrary waveform generator. Again, simultaneously     photonically stimulate the electrodes and the gap between them     using, e.g., the four LEDs capable of 15,000 mcd each through the     ports in the vessel wall described above. The LEDs are preferably     pulse-modulated by frequency-hopping through the following six     frequencies, dwelling at each for five minutes: 464, 1234, 1289,     2008, 3176, and 5000 Hz with 50% duty cycles. The four LEDs were     powered with 14.5 Volts and drew 0.02 amps each, averaged over the     pulse modulation. Continue stimulating concurrently with both     electrical and photonic stimuli at an elevated temperature within     2° C. of the boiling point for at least 40 minutes and preferably     for two or more hours. After two hours, raise the input power to the     vessel to increase the temperature of the solution to within 1° C.     the boiling point. Additionally, monitor the solution temperature     with the thermocouples throughout the process. The surface treatment     protocol should last at least for a duration that provides some     specified minimum number of heat bursts of at least 1° C., e.g., at     least four such bursts.

Here are some representative results from experiments conducted on the dates shown. The protocol evolved over time, as indicated below, culminating in the preferred protocol described above:

Dec. 28, 2008

-   -   The electrodes for this experiment were palladium in a solution         of heavy water. The electrolyte was lithium sulfate and the         silica reagent was anionic silica hydride. The time-varying         electrical stimulus was the sinusoidally modulated pulse stream         described in the aforementioned '287 patent.     -   All data logs with this application show a portion of the         complete data log, focusing on the area of interest when the         reaction was taking place. The portion of data log for the         experiment on this date is shown in FIG. 1. The time scale is         two minutes per division, as it is for all of the data logs         included with this application. Data was logged at ten second         intervals.     -   Traces 108 and 101 show the supply voltage (1V per division) and         supply current (100 mA per division) that were applied to the         heating coil for the duration of the experiment. Trace 103         records the vessel wall temperature (1° C. per division).     -   Traces 107 and 109 show the DC stimulus voltage (2V per         division) and DC stimulus current (15 mA per division), that         were applied to the electrodes for 40 minutes duration after the         baseline temperature of the solution had been reached.     -   Traces 104 and 105 record the respective temperatures (1° C. per         division) from the two thermocouples inside the beaker. The         boiling point for heavy water is 1.4° C. above that for light         water, so the baseline temperature for traces 104 and 105 is         102° C.     -   The two thermocouple traces 104 and 105 were observed to         converge shortly after the DC stimulus was applied, overlay         tightly (“temperature coherence”) during the stimulus, and again         diverge after the stimulus was removed. Note that at least five         “bursts” of heat were recorded by the thermocouple traces 104         and 105. Each heat burst shows a ramp up to a peak and a nearly         symmetrical ramp down. The largest increase was a rise of         1.6° C. to 104.7° in less than four minutes.     -   The electrodes were prepared for testing at Evans Analytical         Group in Sunnyvale, Calif. FIG. 2 is a SEM photo of the surface         of the cathode showing that some portions of it were coated with         a mat deposited from the solution used in the protocol, while         other portions were bare. From above, the deposit looked like a         field of spheres of varying sizes. From the side, it resembled a         row of teeth.     -   Spectral analyses were taken of both the deposited layer and the         bare metal, as shown in. FIGS. 3 and 4. The bare metal was         revealed to be predominantly palladium, with traces of silver.         The presence of silver was not limited to a single site, but was         detected at twenty-three sites by EDS analyses of this sample.         At a later date, we cross-sectioned the same wire electrode and         examined its interior at several places to see if there was any         silver present. As shown in FIG. 5, there was none. We also         tested an untreated wire from the same coil as the piece used in         this experiment for silver on its surface. There was none. We         only found silver at the surface of the treated wire or in the         mat as discussed below.     -   We cross-sectioned the deposited mat with a Focused Ion Beam         (FIB) cut to examine the structure of the “teeth”. As shown in         FIGS. 6 and 7, they are solid rather than hollow, with some         spaces between them. In FIG. 7, one can also clearly see several         strata in the cross section. At the bottom of the picture is the         palladium wire. Then there is a band of palladium that has         separated from the wire and adhered to the inner surface of the         deposited mat. The SEM operator's interpretation of that         separated band is that there may have been either grain growth         or a phase change near the surface of the wire. The mat is at         the top of the picture. The separated palladium adheres         preferentially to the mat above it and there is a very thin         stratum of lighter color at the interface of the separated         palladium and the mat where something else is going on.     -   Note that there are lighter areas between the teeth at some         points on their surfaces. Those were areas where metal was found         to be present between the teeth. The metal areas are raised         approximately 7 μm above the wire surface. Those were areas of         metal that appeared to have seeped or wicked up between the         teeth. FIGS. 8 and 9 show a SEM photo of the metal and an EDS         spectrum taken concurrently showing that metal to consist of         both palladium and silver.     -   The verbs “to seep” and “to wick” above both imply movement by         liquids. If that is actually what is happening here, it is worth         noting that the melting point of palladium is 1555° C. At that         temperature, the cathode would be incandescent, thereby         providing more electrons to stimulate the reaction. The         implications are obvious; that's a very high temperature for a         reaction that is otherwise at or near the boiling point of the         solution, and it is consistent with a nuclear reaction.     -   FIGS. 8 and 9 show a SEM photo of the raised metal and an EDS         spectrum taken concurrently showing that metal to consist of         both palladium and silver. For background electron scattering,         the threshold of detection of an element is generally considered         to be 1% of the sample.     -   FIG. 10 is another EDS analysis of the sample. Note that it         shows the presence of fluorine. This was one of four sites that         showed fluorine to be present. We shall say more about that         below.     -   The SEM operator for most of these measurements has more than         fifteen years experience operating SEM equipment. Although the         EDS spectra lines of palladium and silver are close to each         other, in his opinion, the presence of the silver was         “irrefutable”.

Jan. 3, 2009

-   -   The electrodes for this experiment were palladium in a solution         of heavy water. The electrolyte was lithium sulfate and the         silica reagent was anionic silica hydride. The time-varying         electrical stimulus was the sinusoidally modulated pulse stream         described in the aforementioned '287 patent.     -   The purpose of the experiment was to create a sample for Auger         and Raman testing of its surface.     -   The data logs are shown in FIG. 11. Although we didn't see the         temperature coherence observed in other experiments, there were         some distinct bursts of energy. They were broader and less         abrupt than in some other experiments. One of the two         thermocouples recorded a burst that rose almost 4° C. and lasted         fourteen minutes. Note also that the final burst of heat         occurred after the input power to the heating coil was secured.     -   The summary report from the Auger analysis is shown in FIG. 12.         We will discuss it further below.     -   The Raman testing showed lithium sulfate on the surface, which         was washed away when the sample was rinsed with distilled water.         Curiously, the analysis did not show the presence of silica,         suggesting, according to the operator, that it was either “not         present, or because it was a disordered amorphous SiO_(x)         compound that was not able to produce Raman spectra”.     -   Subsequent EDS testing of this sample did not show evidence of         silver in the palladium, but that may only mean that it was not         present in sufficient amounts to rise above the 1% detection         threshold discussed above.

Jan. 19, 2009

-   -   The experiment was conducted with palladium electrodes in heavy         water. The electrolyte was lithium sulfate and the silica         reagent was anionic silica hydride. The time-varying electrical         stimulus was the sinusoidally modulated pulse stream described         in the aforementioned '287 patent.     -   The data log in FIG. 13 shows replication of the bursts of heat,         as seen by the thermal signatures of the recorded temperatures         (traces 204 and 205). These bursts had exceptional periodicity,         occurring at intervals of approximately thirteen minutes.     -   Note that the temperatures of the heating coil (trace 202) and         the vessel wall (trace 203) drop after each burst, presumably         caused by one or both of the relief valves lifting and venting         some steam. Although the vessel was not observed directly during         any of these experiments because it was enclosed within an         insulated box for safety reasons, venting through the relief         valves would be consistent with the loss of approximately         one-third of the liquid in the vessel during the experiment.     -   Note also that the DC stimulus current (trace 209) spikes         concurrent with or slightly before the bursts occur. Those         current spikes suggest that the resistance between the DC anode         and the common cathode decreased at the same time the         temperature spikes were occurring. (We logged the DC stimulus         voltage and current for most of the experiments. Current         variations were seen in some other cases, but not as large as         those shown here.)     -   FIG. 14 is included to show the one of the EDS results from the         cathode in this experiment. We did not find silver on these         samples, but note the presence of aluminum. We will say more         about that below.

Jan. 30, 2009

-   -   The electrodes for this experiment were palladium in a solution         of heavy water. The electrolyte was lithium sulfate and the         silica reagent was anionic silica hydride. The time-varying         electrical stimulus was the sinusoidally modulated pulse stream         described in the aforementioned '287 patent.     -   This experiment featured four small glass beads threaded onto         the cathode. For example, Hirschberg Schutz & Co., Inc., of         Warren, N.J., markets such beads. The glass beads used in this         experiment proved to have been coated with pure silver by the         manufacturer. The manufacturer makes other glass beads that are         not coated.     -   The data log for the experiment is shown in FIG. 15. The         reaction kicked in at a relatively low temperature (baseline         temperature just above 100° C.) and showed some sustained bursts         lasting as long as five minutes. The temperature of the solution         (traces 304 and 305) peaked at 102.4° C. Note that the         temperature spikes last longer than the ones in the previous         tests, corresponding to more heat being generated with the         threaded beads than with bare wires. There is a strong reaction         before the DC stimulus voltage (indicated by trace 307) was even         applied, indicating that the DC stimulus is optional in the         protocol. For that reason, we only used two electrodes, the RF         anode and the cathode, in most of our later experiments.     -   When viewed in the SEM with the glass beads removed, there were         no deposits on this wire and significant portions of the wire         had spalled and peeled away, again providing evidence of local         high temperatures. FIG. 16 shows a piece of the wire that has         been twisted, as though by extreme heat. FIG. 17 shows a small         piece of palladium that was smooth on one side and textured on         the other. The textured side does not appear to be the result of         shear or etching, and it may have been melted. If that is         verified with additional experiments, it will be very         significant because it would confirm that, with the bead         covering, the electrode attained melting temperature (1555° C.         for palladium).     -   We found numerous Pd fragments had adhered to the surface of the         beads. One site was seen that was predominately palladium, with         silver present in trace amounts.

Feb. 21, 2009

-   -   The electrodes for this experiment were palladium in a solution         of predominately light water. The electrolyte was lithium         sulfate and the silica reagent was anionic silica hydride. The         time-varying electrical stimulus was the sinusoidally modulated         pulse stream described in the aforementioned '287 patent. (The         citric acid solution added to balance the pH in this experiment         was made with heavy water. With less than four drops added into         30 ml of solution, that's why we describe the water as being         “predominately” light.)     -   Glass beads were threaded onto the wire as described above.     -   Because the boiling point of light water is lower than for heavy         water by about 1.4° C., the temperatures were deliberately kept         lower for this experiment to stay just below the lower boiling         point.     -   The data log for the experiment is shown in FIG. 18. Although         the temperatures recorded are lower than those in the previous         experiments with heavy water, the centerline for the two traces         (404 and 405) show the temperature of the solution is still         102° C. There were definite bursts of energy recorded in the         data logs in the now-characteristic thermal signature, although         they were not as regular or robust as the experiments using         heavy water. The temperatures of the heating coil (trace 402)         and the vessel wall (trace 403) drop with the bursts of heat,         again suggesting that the relief valves have lifted.

Feb 28, 2009

-   -   The electrodes for this experiment were silver in a solution of         heavy water. The electrolyte was lithium sulfate and the silica         reagent was anionic silica hydride. The time-varying electrical         stimulus was the sinusoidally modulated pulse stream described         in the aforementioned '287 patent.     -   As shown in FIG. 19, there were again several distinct bursts of         heat (traces 504 and 505) that included the “temperature         coherence” observed with the palladium wire.     -   The wires were tested with SEM and EDS. The silver proved to         have been corroded by the treatment. However, the presence of         fluorine was detected at four sites.     -   The significance of these results is that the contemporary model         regarding LENRs observed in similar electrolytic cells requires         palladium. The crystal lattice of palladium is spacious enough         to absorb both hydrogen and deuterium atoms, thus holding them         in proximity. That model further hypothesizes that this         containment permits adjacent deuterium atoms to interact in ways         that are not otherwise stochastically possible at low         temperatures. These assumptions then imply an interaction that         is believed to permit the deuterium nuclei to get close enough         to each other that they fuse. The protocol described in the         patent referenced above and the present application does not         depend upon that model. Silver does not absorb either hydrogen         or deuterium atoms, so something is happening in the protocol         described herein that must follow a completely different model.         We did not measure the D/Pd atom ratio, so there is no such         experimental evidence to report in that regard.

Mar. 5, 2009

-   -   The electrodes for this experiment were platinum in a solution         of heavy water. The electrolyte was lithium sulfate and the         silica reagent was anionic silica hydride. The time-varying         electrical stimulus was the sinusoidally modulated pulse stream         described in the aforementioned '287 patent.     -   As shown in FIG. 20, there were several distinct bursts of heat         (seen in traces 604 and 605), although the recorded temperatures         did not demonstrate the “temperature coherence” observed with         the palladium and silver wire. The bursts of heat showed a         periodicity of approximately six minutes. Of particular interest         is the fact that after the input power to the vessel (traces 601         and 608) and the stimuli were secured (right side of the data         log), the temperature of the solution continued to rise for more         than eight minutes while the temperature of the heating coil         (trace 602) and the vessel sidewall (trace 603) fell. Clearly,         there was some delayed exothermic reaction occurring inside the         vessel.     -   The cathode from this experiment was examined with SEM and EDS.         The surface of the wire was clean rather than corroded as the         silver had been. No transmutation products were detected. Again,         that may only mean that they were present, but not in sufficient         amounts to rise above the 1% detection threshold.     -   As above with silver, according to the contemporary model for         LENRs, there should not have been any evidence of heat because         of the size of the platinum crystal lattice.

Aug. 9, 2009

-   -   In an effort to test whether the anionic silica hydride and         lithium sulfate in the solution were reacting to produce a form         of lithium silicate, we substituted reagent grade lithium         metasilicate, Li₂SiO₃, for the anionic silica hydride. Because         lithium metasilicate is essentially insoluble in water, it         settled immediately to the bottom of the beaker without         dissolving. We therefore used EDTA (a chelating agent with         surfactant properties) to get some of the lithium metasilicate         to dissolve or suspend in the water. Specifically, we made a         solution consisting of 30 ml of D2O, 350 mg of Li₂SiO₃, 850 mg         of Li₂SO₄, and 700 mg of EDTA. That formed a cloudy solution,         suggesting that the Li₂SiO₃ was either in solution or         suspension. EDTA is acidic, so we buffered the solution with         sodium bicarbonate, NaHCO₃, to bring it back into the pH range         called for in the protocol. After heating and stirring, we added         another 350 mg of EDTA and buffered again with NaHCO₃. The         electrodes were palladium.     -   The data log for this experiment is shown in FIG. 21. The         boiling point of this solution was higher than that in the         standard protocol, so the centerline of the two traces (704 and         705) for the thermocouples is 104° C. There were some bursts of         heat, but they were not periodic. One of those bursts was almost         1° C. in less than ten seconds.     -   The electrodes used in this experiment were later analyzed with         SEM and EDS. There was a crystalline coating on the cathode that         included carbon, oxygen, sodium, silicon, and sulfur. The         coating was not as well organized as that shown on some of the         earlier SEMS.     -   The pH of the solution at the beginning of the experiment was         7.45. At the end, it was 9.70, so it is apparent that some         chemical reaction took place in the solution during the course         of the experiment.

Aug. 15, 2009

-   -   In a further effort to confirm that silica was a critical part         of the protocol, we conducted another experiment with 30% sodium         silicate (“water glass”), Na₂SiO₃, as the source of the         silicate. Na₂SiO₃ is readily soluble in water, producing an         alkaline solution. The sodium silicate tended to congeal at         higher temperatures, so we finally used only one drop of it in         30 ml. of heavy water. The other ingredients were 350 mg of         Li₂SO₄ and 150 mg of EDTA. This yielded a highly acidic solution         that we again buffered into the desired range of 6.9 to 8.9 with         sodium bicarbonate. The electrodes were palladium, and the         time-varying electrical stimulus was the sinusoidally modulated         pulse stream described in the aforementioned '287 patent.     -   A portion of the data log for this experiment is shown in         FIG. 22. Again, the centerline for the thermocouple traces (804         and 805) was 104° C., because the boiling point of this solution         was higher than that of the solution in the standard protocol.         There were a small number of bursts of heat during the         experiment. These heat bursts were rather feeble, but         nevertheless were present.     -   A SEM photo and the accompanying EDS spectrum are shown in         FIG. 23. Note the presence of magnesium, which could either be a         transmutation product of sodium or a contaminant. We did not         test the raw materials in this experiment for contaminants.

Nov. 15, 2009

-   -   The electrodes, for this experiment were palladium in a solution         of heavy water. The electrolyte was lithium sulfate and the         silica reagent was lithium metasilicate, Li₂SiO₃. The         time-varying electrical stimulus was the sinusoidally modulated         pulse stream described in the aforementioned '287 patent.     -   This was a version of the protocol intermediate between the one         described in the described in the '287 patent and the one         described above.     -   The cell began to respond much more rapidly than previous         experiments. FIG. 24 shows the data log for this experiment. The         pulses of heat were not very large, but there were many of them,         and they tended to repeat every three to five minutes.     -   The electrodes from this experiment were analyzed with SEM and         EDS. They proved to be relatively clean and showed no evidence         of transmutation products.

Dec. 31, 2009

-   -   The electrodes for this experiment were palladium in a solution         of heavy water. The protocol in this experiment was the one         described above as the preferred embodiment of the invention.         This experiment included glass beads on one of the electrodes;         these beads were not coated in silver.     -   The data logs of the experiment are shown in FIG. 25. Some         smaller burst of heat had preceded the portion of the data log         shown in that figure. The large burst shown in the figure raised         one of the thermocouples approximately 2° C. in twenty seconds         and lasted more than six minutes.     -   FIG. 26 shows a site in a SEM photo of one of the palladium         electrodes from this date. Lighter areas of palladium are         radiating from a central point. There was no difference between         the lighter areas and the neighboring surface in EDS analysis.         This was one of several sites with a similar appearance on this         sample that show what could be ejecta from a localized burst of         heat on the wire.     -   There is also a piece of wire that has separated at the right         side of the photo. It partially covers a deposit of sulfate that         was laid down during the protocol, indicating that the         separation occurred during or after the protocol. There is no         indication that mechanical action caused the separation, so it         may have been caused by thermal stresses.     -   Note that if there was a localized burst of heat on the wire         sufficient to melt, or even to vaporize, the palladium, it would         also be intense enough to vaporize the water in the immediate         vicinity, forming a burst of steam. That burst of steam would         expand out from the origin of the heat in a compression shock         wave until it lost heat to the surrounding solution. At some         point it would collapse back upon the center. When the bubble         collapsed back, it could press the ejecta back upon the surface         of the wire in the manner shown in the picture.     -   Roger Stringham has reported on Pd/D₂O cavitation experiments         that yield transient bubbles in such a manner. He has shown that         the bubble originates in a fusion event within a palladium         lattice and contains D₂O, D₂, and O₂ and describes the dynamics         of the high-energy transient bubbles in detail. His report can         be found at this URL:         http://www.lenrcanr.org/acrobat/StringhamRcavitationb.pdf.     -   We rinsed the electrode tested above in distilled water to         remove the sulfate and re-examined it. The later testing did not         show pore sites of ejecta and the radial patterns were no longer         visible.

Taken together, we believe the experiments conducted with anionic silica hydride, lithium metasilicate, and sodium silicate support the reasoning that silica is critical to the reaction and that lithium silicate promotes a stronger reaction.

One of the things that caught our attention in the experiments above was the frequent indication of fluorine in the EDS analyses. The Feb. 28, 2009, experiment showed F at four sites. Several samples showed traces of aluminum and one showed gallium at multiple sites. Flanagan's anionic silica hydride includes several additives. His “Mega H” powder contains potassium citrate (K₃C₆H_(S)O₇), potassium carbonate (K₂CO₃), and oleic acid (C₁₈H₃₄O₂). His “Super Hydrate” solution also contains potassium carbonate and oleic acid, plus magnesium sulfate (MgSO₄). We tested Flanagan's products with EDS analysis to clarify the ingredients of the protocol. Sodium and copper were found to also be present, although they were not disclosed as ingredients on the product labels. Lithium sulfate (Li₂SO₄) is used in our protocol as an electrolyte. However, the identified original ingredients for the protocol do not account for the presence of fluorine, aluminum and gallium in the post-experiment EDS analyses.

Now return to FIG. 12, the Atomic Concentration Table from the Auger analysis of the Jan. 3, 2009 experiment. Note the presence of nitrogen, aluminum, chlorine, and copper. Each of these is a transmutation product of one of the ingredients in the protocol. Specifically:

-   -   ₆C transmutes into ₇N     -   ₁₂Mg transmutes into ₁₃Al     -   ₁₆S transmutes into ₁₇Cl     -   ₂₉Cu transmutes into ₃₀Zn

Further, the ₉F found above in the EDS analyses is the transmutation product of ₈O.

If hydrogen or lithium had transmuted to helium and beryllium, EDS would not have detected them, which does not detect elements with atomic numbers below five.

We cannot account for the presence of gallium in the one sample.

We now have found strong evidence of transmutation products of six different elements using two different EDS systems, with aluminum having been found with both of them. Taken together, the data supports a strong claim that our protocol has induced nuclear reactions on numerous occasions. While that claim will doubtless be controversial, we assert that the evidence for it is strong.

The nature and shape of the bursts of heat recorded in our data logs, together with the condition of the electrode surfaces seen from SEM analyses, indicate that the surface temperature of the electrodes may locally approach or even attain the 1555° C. melting point of palladium, such that the solution at the surface of that electrode can locally flash to steam. A continuous reaction requires the on-going replenishment of solution in the liquid phase, which naturally occurs in the test reaction vessel. An alternative protocol may be to provide fresh solution at that inlet of a nozzle where the steam is exhausted. Finally, there is no evidence in any of our experiments that the exothermic reaction being induced is anything other than a surface effect. Given the apparent energy densities of that reaction, that could be very important because it indicates that, for whatever reason, the reaction is self-limiting to the surface area of the electrodes. 

1. A method of preparing materials at or near their surfaces, comprising: preparing a solution of an electrolyte in a liquid; heating and maintaining the solution at an elevated temperature to within 5° C. of the boiling point in a sealed vessel; electrically stimulating two or more conductive electrodes immersed within the solution over an extended time period by applying a voltage between electrodes, at least one of the electrodes having a surface to be treated thereby and in intimate contact with a source of silica; and photonically stimulating the solution with illumination from a light source.
 2. The method as in claim 1, wherein the liquid for the solution comprises water.
 3. The method as in claim 2, wherein the water is predominantly light water (H₂O).
 4. The method as in claim 2, wherein the water is a combination of light water (H₂O) and heavy water (D₂O).
 5. The method as in claim 2, wherein the water is predominantly heavy water (D₂O).
 6. The method as in claim 1, wherein the electrolyte comprises a lithium salt.
 7. The method as in claim 6, wherein the lithium salt comprises lithium sulfate (Li₂SO₄).
 8. The method as in claim 1, wherein a surfactant is added to the solution.
 9. The method as in claim 1, wherein a buffering agent is added to the solution so as to maintain a pH in a range from 6.5 to 8.9.
 10. The method as in claim 9, wherein the buffering agent is EDTA.
 11. The method as in claim 9, wherein the buffering agent is citric acid.
 12. The method in claim 1, wherein the solution in the sealed vessel is heated above its boiling point at atmospheric pressure and its pressure rises above one standard atmosphere.
 13. The method as in claim 1, wherein the sealed vessel comprises a glass- or silica-lined metallic vessel with ports for the metallic electrodes and for one or more thermocouples.
 14. The method as in claim 1, wherein the solution in the sealed vessel is blanketed with a gas.
 15. The method as in claim 14, wherein the gas comprises hydrogen, helium, or a combination thereof.
 16. The method as in claim 14, wherein the solution is saturated with the blanketing gas.
 17. The method as in claim 1, wherein the conductive electrodes are metal.
 18. The method as in claim 17, wherein the metal comprises one or more of palladium, silver, platinum and gold.
 19. The method as in claim 17, wherein the conductive electrodes are of the same metal.
 20. The method as in claim 17, wherein the conductive electrodes are of dissimilar metals.
 21. The method as in claim 1, wherein at least one of the electrodes is a conductive material other than metal.
 22. The method as in claim 1, wherein at least one of the electrodes is coated with silica.
 23. The method as in claim 1, wherein at least one of the electrodes is coated with a silicate.
 24. The method as in claim 1, wherein a source of the silica in contact with the electrodes comprises a silica compound in suspension in the water.
 25. The method as in claim 24, wherein a chelating agent facilitates the suspension of the silica compound.
 26. The method as in claim 25, wherein the chelating agent is EDTA.
 27. The method as in claim 1, wherein a source of the silica comprises a lithium silicate.
 28. The method as in claim 1, wherein a source of the silica in contact with the electrodes comprises a silica compound in solution.
 29. The method as in claim 28, wherein the silica compound in solution comprises an anionic silica hydride.
 30. The method as in claim 29, wherein the anionic silica hydride comprises a silsesquioxane composition.
 31. The method as in claim 1, wherein a source of the silica comprises one or more silica or glass beads threaded over the one or more electrodes being surface treated.
 32. The method as in claim 1, wherein a source of silica lies within the composition of the electrode.
 33. The method as in claim 32, wherein a source of silica comprises an electrode consisting of sintered metal and silica.
 34. The method as in claim 1, wherein a source of silica includes a silica or glass lining of the sealed vessel.
 35. The method as in claim 1, wherein the sealed vessel is lined with a piezoelectric material.
 36. The method as in claim 35, wherein the piezoelectric material is a porcelain glaze.
 37. The method as in claim 1, wherein the electrical and photonic stimuli are applied concurrently.
 38. The method as in claim 1, wherein the electrical and photonic stimuli are applied sequentially.
 39. The method as in claim 1, wherein the electrical stimulation is a direct current voltage.
 40. The method as in claim 1, wherein the electrical stimulation is an alternating current voltage.
 41. The method as in claim 40, wherein the alternating current voltage has frequencies in the RF range.
 42. The method as in claim 41, wherein the alternating current voltage has frequencies coinciding with absorptive spectra of components in the solution.
 43. The method as in claim 1, wherein the electrical stimulation comprise an RF comb of spectra with spaced peaks in a range of 1 MHz to 200 MHz, at least some of said peaks coinciding with molecular vibrational resonance frequencies in the solution.
 44. The method as in claim 1, wherein the electrical stimulation comprises a sinusoidal signal have a frequency between 1 MHz and 20 MHz added to another sinusoidal signal having a frequency between 25 MHz and 100 MHz.
 45. The method as in claim 1, wherein the electrical stimulation comprises a replication of electrical energy emitted during a desired exothermic reaction.
 46. The method as in claim 45, wherein the electrical stimulation replicates the emitted energy but with greater amplitude.
 47. The method as in claim 1, wherein the electrical stimulation is a direct current voltage and an alternating current voltage applied concurrently between separate anodes and a common cathode.
 48. The method as in claim 1, wherein the electrical stimulation is a direct current voltage and an alternating current voltage applied concurrently between a common anode and a common cathode.
 49. The method as in claim 1, wherein the electrical stimulation is a direct current voltage and an alternating current voltage applied sequentially between separate anodes and a common cathode.
 50. The method as in claim 1, wherein the electrical stimulation is a direct current voltage and an alternating current voltage applied sequentially between a common anode and a common cathode.
 51. The method as in claim 1, wherein the light source providing the photonic stimulation of the solution is modulated.
 52. The method as in claim 51, wherein the light source is square-wave modulated.
 53. The method as in claim 51, wherein the light source is pulse-modulated.
 54. The method as in claim 51, wherein the light source is modulated with a frequency that varies or hops.
 55. The method as in claim 1, wherein the light source providing the photonic stimulation of the solution comprises a set of intensity-modulated light emitting diodes directing light pulses into the solution.
 56. The method as in claim 55, wherein the light emitting diodes are white.
 57. The method as in claim 1, wherein the electrical and photonic stimulation are provided over an extended time period of at least 40 minutes and in which at least a specified number of heat bursts have been detected.
 58. The method as in claim 1, wherein the combination of electrical and photonic stimulation of the electrodes and electrolytic solution is such as to stimulate a quantum effect that affects the wave-particle duality of the electrons as they migrate across the solution toward the electrodes.
 59. The method as in claim 1, wherein the combination of electrical and photonic stimulation of the electrodes and electrolytic solution is such as to modify the surface of at least one of the electrodes so as to facilitate electron tunneling at that surface. 